EP0944664B1 - Resine susceptible de durcir a temperature ambiante - Google Patents

Resine susceptible de durcir a temperature ambiante Download PDF

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Publication number
EP0944664B1
EP0944664B1 EP96944790A EP96944790A EP0944664B1 EP 0944664 B1 EP0944664 B1 EP 0944664B1 EP 96944790 A EP96944790 A EP 96944790A EP 96944790 A EP96944790 A EP 96944790A EP 0944664 B1 EP0944664 B1 EP 0944664B1
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EP
European Patent Office
Prior art keywords
mol
curable composition
unsaturated
group
equivalent weight
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EP96944790A
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German (de)
English (en)
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EP0944664A1 (fr
Inventor
Dieter Barucha
Dean M. Moren
Manfred Stepputtis
Frank Y. Xu
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3M Co
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Minnesota Mining and Manufacturing Co
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule

Definitions

  • This invention relates to room temperature curable resin systems that are obtainable by a Michael reaction of a compound having two or more ⁇ , ⁇ -unsaturated groups and a Michael donor in the presence of a suitable catalyst.
  • the obtained cured compositions are suitable for use in electrical applications and in particular for insulation of electrical splices.
  • curable resin systems where the crosslinking mechanism is based on polyurethane chemistry have been used.
  • hydroxyl-bearing oligomers such as polyether polyols are crosslinked using low molecular weight polyfunctional isocyanate compounds.
  • Epoxy resins also commonly used for splices, require the use of stoichiometric amounts of amine-containing hardeners. Replacement of isocyanate-containing and amine-containing systems with less objectionable systems is a long-standing need.
  • US 5,132,367 describes NCO-free resins and cured products thereof.
  • the cured products are obtained by a Michael reaction of an acetoacetylated (meth)acrylic resin or an acetoacetylated polyester and an NCO-free polyurethane having at least two (meth)acrylic end groups.
  • US 5,132,367 however does not teach the use of these products in electrical applications.
  • EP 227454 discloses a process for preparing a cured polymer involving the Michael reaction of an acetoacetylated polyol and a poly ⁇ , ⁇ -unsaturated ester.
  • the obtained cured products are said to exhibit excellent adhesion, excellent solvent resistance, excellent gloss retention, good flexibility and hardness.
  • US 5,459,178 describes foundry mixtures comprising an acetoacetate ester, an ⁇ , ⁇ -ethylenically unsaturated monomer and a liquid tertiary amine catalyst.
  • a cured system is obtained by reacting these components.
  • the acetoacetate ester used is prepared by transesterification of polyhydroxyl compound having an average of at least two hydroxy groups with an alkylacetoacetate.
  • DE 3508399 corresponding to US 4,871,822 discloses a Michael reaction of olefinically unsaturated compounds with compounds containing at least two active hydrogens for 2 component lacquers.
  • olefinically unsaturated compounds there are considered compounds having at least two ⁇ , ⁇ -unsaturated carbonyl groups.
  • Michael donors there are considered a large number of compounds amongst which are acetoacetylated polyols or polyamines and such compounds as e.g. acetylacetone or benzoylacetone.
  • WO 95/16749 describes a water-borne curable composition that comprises an acetoacetylated polymer in the form of an aqueous solution, dispersion or emulsion and a polyacrylate that has at least two (meth)acrylate end groups. According to this publication, such composition is stable even in the presence of a catalyst until the water is evaporated from the system.
  • thermosetting systems The use of acetoacetyl chemistry, in particular the use of acetoacetylated resin, in thermosetting systems is further described in Journal of Coatings Technology Vol. 61 no. 771 page 31 to 37; Journal of Coatings Technology Vol. 65 no. 821 page 63 to 69; Surface Coatings Australia, September 1989 page 6 to 15; and Journal of Coatings Technology Vol. 61 no. 770 page 83 to 91.
  • room temperature is meant a temperature of about 5°C to about 30°C, in particular from about 10°C to about 25°C.
  • the present invention provides the use of a curable composition for electrical applications, said curable composition comprising (i) a compound having at least two ⁇ , ⁇ -unsaturated groups and an equivalent weight of less than 250 g/mol, (ii) a catalyst capable of initiating a Michael reaction and (iii) a Michael donor having an equivalent weight of less than 250 g/mol.
  • This invention also provides a package containing constituents of a curable composition, said package comprising two compartments, one of said compartments comprising a Michael donor having an equivalent weight of less than 250 g/mol and a compound having at least two ⁇ , ⁇ -unsaturated groups and an equivalent weight of less than 250 g/mol and the other compartment comprising a catalyst capable of initiating a Michael reaction.
  • the invention also provides the use of the above package for electrical applications, in particular for insulation of electrical splices.
  • the present invention provides curable compositions.
  • a curable composition comprising (i) a compound having at least two ⁇ , ⁇ -unsaturated groups and an equivalent weight of less than 250 g/mol, (ii) a catalyst capable of initiating a Michael reaction and (iii) a Michael donor having an equivalent weight of less than 250 g/mol can be effectively cured at room temperature to provide cured products that have appropriate electrical properties for use in electrical applications and in particular for insulating electrical splices in low or medium voltage applications.
  • Equivalent weight in connection with the present invention is defined as the molecular weight of a compound divided by the number of reactivities of the compound that are relevant to the Michael reaction.
  • Michael donor in connection with the present invention means a nucleophilic reactant, in particular a carbon or nitrogen nucleophilic reactant, in a Michael reaction.
  • Michael reaction in connection with the present invention means the addition of a nucleophilic reactant to a generally activated ⁇ , ⁇ -unsaturated group.
  • ⁇ , ⁇ -unsaturated group means a functional group that is sufficiently activated to act as an acceptor, i.e. an electrophilic group, in a Michael reaction.
  • a curable composition is used for insulating electrical splices, in particular those of the low or medium voltage type.
  • This use generally involves filling a mold body that contains the electrical splice with a curable composition according to the present invention and then allowing it to cure, preferably at ambient temperature. It was found that the cured composition obtained generally has a shore A hardness of more than 60 and very good electrical properties. In particular a high volume resistivity of more than 10 10 Ohm cm (at room temperature) and an electrical resistance of more than 1000 M Ohm could be obtained between two phases of an electrical splice.
  • cured compositions can be obtained that are capable of withstanding fluctuating temperature and humidity conditions to which electrical splices, in particular underground splices, are frequently exposed. Additionally, the curable compositions showed no substantial foaming in the presence of water making it easier to fill a mold body without generation and inclusion of gas bubbles. Such gas bubbles when present tend to decrease the electrical properties of an insulated splice.
  • the compound has at least two ⁇ , ⁇ -unsaturated groups, (hereinafter also referred to as ⁇ , ⁇ -unsaturated compound) preferably two ⁇ , ⁇ -ethylenically unsaturated groups. Particularly preferred are compounds having at least two and more preferably at least three ⁇ , ⁇ -unsaturated carbonyl groups. Preferably, such ⁇ , ⁇ -unsaturated carbonyl groups are acrylic or methacrylic groups. It was further found that improved electrical properties in the cured system are obtained when the molecular weight of the ⁇ , ⁇ -unsaturated compound decreases and the reactive functionality increases.
  • curing of the composition is preferably carried out at ambient temperature. Curing in a system involving low molecular weight and highly functional reactants at ambient temperature generally leaves a large number of reactive groups unreacted. This in turn causes the curing reaction to continue especially in the vicinity of the cables since electrical current flowing through the cables causes some increase in temperature. As a consequence, the splice will have a higher cross-linking density at the vicinity of the cables and lower near the outer region of the mold. Fluctuating environmental conditions such as temperature and humidity may thus cause mechanical stresses in the splice causing cracking at boundaries of completely cross-linked regions and less cross-linked regions.
  • the equivalent weight of an ⁇ , ⁇ -unsaturated (carbonyl) compound in connection with this invention is less than 250 g/mol and more preferably less than 200 g/mol.
  • a particularly preferred range of equivalent weight is between 30 g/mol and 150 g/mol.
  • Suitable ⁇ , ⁇ -unsaturated compounds are ⁇ , ⁇ -unsaturated ketones, ⁇ , ⁇ -unsaturated esters, ⁇ , ⁇ -unsaturated aldehydes, ⁇ , ⁇ -unsaturated amides, ⁇ , ⁇ -unsaturated carboxylic acids, ⁇ , ⁇ -unsaturated nitriles, ⁇ , ⁇ -unsaturated sulfoxides, ⁇ , ⁇ -unsaturated sulfones, ⁇ , ⁇ -unsaturated nitro compounds, ⁇ , ⁇ -unsaturated phosphonates, ⁇ , ⁇ -unsaturated phosphoranes and the like, in particular 1,6-hexanediol diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane-tetraacrylate, ditrimethylo
  • a suitable catalyst for the Michael reaction is a base of which the conjugated acid preferably has a pK a between 12 and 14
  • Most preferably used bases are organic. Examples of such bases are 1,4-dihydropyridines, methyl diphenylphosphane, methyl di-p-tolylphosphane, 2-allyl-N-alkyl imidazolines, tetra-t-butylammonium hydroxide, 1,8-diaza-[5.4.0]-bicycloundecene, potassium methoxide, sodium hydroxide, and the like.
  • a highly preferred catalyst in connection with this invention is tetramethylguanidine.
  • the amount of catalyst used in a curable composition in accordance with the present invention is preferably between 0.05% by weight and 2% by weight more preferably between 0.1% by weight and 0.6% by weight.
  • a Michael donor in connection with the present invention preferably corresponds to one of formulas (I) to (III): (W 1 -CHR 1 -W 2 ) x -P (W 1 -NH-W 2 ) x -P W 1 -CH 2 -W 2 wherein
  • Particularly preferred Michael donors according to formula (I) are acetoacetylated polyols.
  • the acetoacetylated polyol can be prepared by transesterification with an alkyl acetoacetate.
  • a preferred transesterification reagent for this purpose is tertiarybutyl acetoacetate described by J.S. Witzeman and W.D. Nottingham of Eastman Kodak Company at Chemspec USA 89 Symposium.
  • the polyols being acetoacetylated in this invention preferably have 2 or more hydroxy groups.
  • the conversion of hydroxy groups to acetoacetate groups should be between 80 mol % and 100 mol % and more preferably between 85 mol % and 100 %.
  • Suitable acetoacetylated polyols are for examples those obtained from one of the following polyols: pentaerythritol, trimethylolethane, trimethylol propane, ditrimethylol propane, K 55 available from Bayer AG which is a condensation product of trimethylolpropane and propyleneoxide, dipentaerythritol, castor oil, glycerine, dipropyleneglycole, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylendiamine, neopentylglycole, propanediol, butanediol, diethyleneglycole and the like.
  • an acetoacetylated polyol in connection with this invention has an equivalent weight of less than 200 g/mol.
  • a preferred range of equivalent weight of an acetoacetylated polyol in connection with this invention is between 30 g/mol and 150 g/mol.
  • Michael donors according to fomula (II) are e.g. compounds of the type p.CH 3 -(C 6 H 4 )-SO 2 NHCOO-G wherein G represents the residue of a polyol such as e.g. pentaerythritol, trimethylolpropane, 1,6-hexanediol, ditrimethylolpropane, propanediol, diethyleneglycole and the like.
  • G represents the residue of a polyol such as e.g. pentaerythritol, trimethylolpropane, 1,6-hexanediol, ditrimethylolpropane, propanediol, diethyleneglycole and the like.
  • Examples of compounds according to formula (III) are NC-CH 2 CN, CH 3 SO 2 CH 2 CN, CF 3 -CO-CH 2 CO-CF 3 , CF 3 -CO-CH 2 -CO-OC 2 H 5 , p-CH 3 C 6 H 4 SO 2 CH 2 SO 2 CH 3 , C 6 H 5 -CO-CH 2 -SO 2 CH 3 , (CH 3 O 2 CCH 2 ) 2 SO 2, p-O 2 NC 6 H 4 CH 2 CN, and the like. Further examples may be found in U.S. Patent No. 5,256,473.
  • a particularly preferred type of Michael donor corresponding to formula (III) for use in this invention corresponds to the following formula (IV): R-CO-CH 2 -CO-R' wherein R and R' each independently represent an aryloxy group, an alkoxy group, an alkyl group or an aryl group.
  • a Michael donor according to formula (III) and in particular formula (IV) is being preferred because they are generally less costly than e.g. an acetoacetylated polyol which requires an acetoacetylation of a polyol as described above. Moreover, this acetoacetylation involves a transesterification during which an alcohol is formed as a waste.
  • Preferred Michael donors according to formula (IV) are those wherein R and R' are independently selected from a substituted or an unsubstituted alkyl such as e.g. methyl, ethyl, propyl, an unsubstituted or substituted aryl such as e.g. a phenyl, a substituted or unsubstituted alkoxy group such as e.g.
  • aryloxy group such as e.g. a phenoxy group.
  • Examples of compounds according to formula (IV) are acetylacetone, methylacetoacetate, ethylacetoacetate, methyl malonate, ethyl malonate, t-butyl acetoacetate, and the like.
  • Michael donor and ⁇ , ⁇ -unsaturated compound in stoichiometric amounts. It is, however, possible to deviate from the stoichiometric amounts and a practical working ratio of Michael donor to ⁇ , ⁇ -unsaturated compound is between 1 and 1.5.
  • a curable composition in connection with the present invention may include further components such as a filler and/or a thickener.
  • a filler has the advantage that the total cost of the composition can be reduced without substantially reducing the properties and in particular the electrical properties of the cured polymer obtained from the composition.
  • the amount of filler may vary over a wide range but is preferably between 10 and 75% by weight and more preferably between 15 and 65% by weight. It has further been found that crack formation in electrical splices under fluctuating temperature and humidity conditions that is sometimes observed with a cured product obtained from a composition that comprises high functionality and low molecular weight reactants e.g. with an acetoacetylated polyol in accordance with this invention can be avoided when the composition includes at least 50% by weight of filler.
  • Suitable fillers that can be used in connection with the present invention include organic and/or inorganic fillers such as feldspar, silica, glass bubbles, sand, talc, aluminium hydroxide, thermoplastic powders, caoline, silicium dioxide, aluminium silicates, magnesium silicates, particulate polymeric fillers, glass beads and glass microbubbles, ceramic particles, magnesium carbonate calcium carbonate, and the like.
  • organic and/or inorganic fillers such as feldspar, silica, glass bubbles, sand, talc, aluminium hydroxide, thermoplastic powders, caoline, silicium dioxide, aluminium silicates, magnesium silicates, particulate polymeric fillers, glass beads and glass microbubbles, ceramic particles, magnesium carbonate calcium carbonate, and the like.
  • a thickener to the composition so as to obtain a viscosity between 1000 and 5000 centipoise. If the composition has too low a viscosity, it may leak from a mold and special precautions to avoid such leaking would then be needed. On the other hand, if the viscosity becomes too high, it may be difficult to fill a mold without the inclusion of air bubbles.
  • Suitable thickeners for use in a composition in connection with this invention are preferably compatible with the composition and include for example solid ketone-resins, solid urea resins, solid formaldehyde resins and solid epoxy resins. An adhesion promoting agent is optionally present to insure good adhesion of the resin matrix to the embedded electrical splice.
  • adhesion-promoting agents such as vinyltrimethoxysilane, vinyltriethoxysilane and aminopropyltriethoxysilane have been found to be particularly effective. Particularly preferred is aminopropyltriethoxysilane (SilquestTM A1100 available from Osi Specialties).
  • the adhesion promoting agent can be added to the composition in amounts of 0.3 to 4.0 weight percent, preferred is about 1 to about 3, with 1% being most preferred.
  • the composition may also contain a plasticizer.
  • Plasticizers that can be used in the present invention are for example hydrocarbon resins, phthalates, e.g. dialkyl phthalates, polybutenes, liquid paraffins, vegetable oils, naphthenic acids, adipates, glutarates, benzoates, etc.
  • a preferred plasticizer is dioctyl adipate.
  • Curable compositions in connection with the present invention are preferably substantially free of solvents and readily pourable at ambient temperature in particular when the application is intended for insulation of electrical splices.
  • Curable compositions in connection with the present invention generally have a pot life between 10 and 60 minutes so that there is sufficient handling time of the composition once it has been prepared.
  • a curable composition in connection with the present invention is prepared by mixing two parts together.
  • One part contains the catalyst and the other contains the reactants, i.e. the ⁇ , ⁇ -unsaturated compound and the Michael donor.
  • reactants i.e. the ⁇ , ⁇ -unsaturated compound and the Michael donor.
  • the catalyst together with one of the reactants in one part and having the other reactant in the other part these embodiments generally produce inferior results, presumably because reaction of the catalyst with the reactant can take place. The extent of this reaction will generally depend on the kind of catalyst and reactants used.
  • a package containing the constituents of a curable composition, the package comprising two compartments, one of the compartments comprising a Michael donor according to this invention and a compound having at least two ⁇ , ⁇ -unsaturated (carbonyl) groups.
  • the other compartment comprises a suitable catalyst for the Michael reaction. It is further preferred to have a thickener added to this latter compartment. Further, a filler may be added to the compartment containing the catalyst and/or the filler may be added to the compartment holding the reactants.
  • US 3,074,544 discloses a multiple compartment flexible unitary package for compartmentalised accommodation and selective admixture of at least two fluent materials, comprising a normally flat envelope of strong flexible heat sealable sheet material, two opposing sidewalls of said envelope being joined by heat sealing to form a transversely extending rupturable seam separating the interior of said envelope into individual compartments, the seam including masking means in the form of a substantially uniformly open web interposed between sidewalls and through the openings of which the sidewalls are heat sealed, said web reducing to substantially less than its total area, the area of the seam over which joinder of the sidewalls is effected.
  • a further suitable package for use in connection with this invention is described in for example DE-A 4239288. It comprises a surrounding bag with two portion bags therein. The contents of these portion bags is kept separate by a clamp. By removing the clamp, the contents can be mixed together in the surrounding bag. A good mixing can be obtained by kneading the surrounding bag and contact with the chemicals is avoided. After mixing, the surrounding bag can be opened and the ready composition can then be used. Accordingly, the use of a package in accordance with the present invention involves mixing the contents of the compartments together and subsequently using the resulting composition in an electrical application as set out above.
  • a curable composition can be poured in a mold containing an electrical splice. Subsequently, the curable composition is allowed to cure in the mold so as to obtain in insulated electrical splice.
  • Samples were in the form of 1 mm thick sheet of sufficient dimension to cover the electrode surface. Resin samples were cured at 23 °C for 24 hours, followed by 24 hours at 80 °C before measurements were made.
  • a low-voltage in-line splice is prepared.
  • Four separate wires have a cross-section of 150 sq. mm are spliced using standard methods.
  • the splice is then covered with a large two-part polymeric mold body having a length of approximately 500 mm and a circumference at its largest part of about 350 mm.
  • curable composition Approximately four kilograms of curable composition was prepared as described in the examples and poured into the mold body, thus encapsulating the splice in resin.
  • the completed low-voltage in-line splice denoted hereinafter as a loop, was subjected to a variety of conditions designed to simulate long term environmental exposure. Electrical resistance was measured after the tests. A large amount of data is generated from these tests, including several different phase-to-phase measurements and phase-to-water measurements. An average value describing the overall electrical resistance is given. This should be considered as a relative measurement used for comparative purposes only.
  • Viscosity of the curable composition was measured by cone and plate geometry viscometry using a Model CV 20 N Viscometer manufactured by Haake (Karlsruhe, Germany) with a Pk 45-4° cone. Results were recorded in units of milliPascal seconds (mPs).
  • Acetoacetylated polyols were prepared according to the following general procedure:
  • the selected polyol and the acetoacetylating compound (TBAA was used), also called transesterification reagent, were added to a reaction kettle equipped with a stirrer and a distillation column connected to a vacuum line. Amounts of polyol and transesterification reagent were selected in accordance with a desired conversion degree of the polyol with 85 mol% being obtained when the polyol and transesterification reagent were used in stoichiometric amounts. A 100 mol% conversion was obtained using the transesterification reagent in a molar excess of 1/3. The relationship between conversion and amounts of reactants was determined by quatitative IR-spectroscopy and quantitative analysis of the alcohol that is released during the reaction.
  • the reaction was carried out at 150 °C for 1 hour and during the next two hours the temperature was raised stepwise to 170 °C. The reaction was continued at this temperature until no more alcohol released. The receiver was then removed and a vacuum was applied to remove any residual alcohol which was trapped in a carbondioxide ice bath. The combined quantities of destilled and trapped alcohol yield the total amount of released alcohol.
  • This example shows the effect of the equivalent weight of the acetoacetylated polyol on the properties of the obtained cured composition (conversion degree of the acetoacetylated polyols was 85 mol% in each of the compositions).
  • the following curable compositions were prepared and allowed to cure at ambient temperature for 24 hours and subsequently at 80 °C for 24 hours. All parts listed are by weight.
  • the mechanical and electrical properties of the cured compositions were subsequently determined using the above test methods.
  • Composition 1-A Pentaerythrit (AcAc) 4 (equivalent weight 59 g/mol) 34 parts SR 355 66 parts TMG 0.5 parts
  • Composition 1-B K55 (AcAc) 3 (equivalent weight 116g/mol) 50 parts SR 355 50 parts TMG 0.3 parts
  • Composition 1-C PPG 1000 (AcAc) 2 (equivalent weight 292g/mol) 72 parts SR 355 28 parts TMG 0.3 parts
  • composition 1-D is a composition of Composition 1-D:
  • composition SCOTCHCAST® (3M Company) based on isocyanate crosslinking.
  • Mechanical and Electrical Properties 1-A 1-B 1-C 1-D Tensile strength (N/mm 2 ) 18 16 0.6 15 Elongation at break (%) 2 15 32 75 Dielectric Strength (kV/mm) 28 28 23 24 Loss factor room temperature 0.009 0.03 0.13 0.05 50 °C 0.009 0.14 0.46 0.08 80 °C 0.01 0.18 0.68 0.13 Permittivity room temperature 4.1 4.4 7.2 4.6 50 °C 4.3 7.2 11.2 5.8 80 °C 4.4 9.4 18.0 7.2
  • composition 1-C the equivalent weight of the acetoacetylated polyol becomes more than 250 g/mol (composition 1-C)
  • composition 1-D the properties of the cured composition are approximately equal to that of an isocyanate containing system (1-D) and in some cases are even better.
  • little dependence of the loss factor and permittivity is seen for composition 1-A.
  • This example shows the influence of the conversion degree of the polyol and the influence of the relative amounts of the reactants.
  • Cured compositions were prepared in accordance with the procedure set out in example 1 using the curable compositions shown in the following Table 3A.
  • Table 3B shows the mechanical properties of the cured compositions.
  • compositions Ingredient Conversion degree (mol%) Composition Number 3-A 3-B 3-C 3-D 3-E 3-F K55(AcAc) 3 100 50 - - 57 - - K55(AcAc) 3 85 - 50 - - 57 - K55(AcAc) 3 70 - - 50 - -
  • This example shows the results obtained with a curable composition containing a compound according to formula (IV).
  • a curable composition was prepared by mixing 100 parts A with 22 parts B.
  • the obtained curable composition after 3 minutes of mixing had a viscosity of 2600 mPs and was subsequently cured in accordance with the procedure of example 1.
  • PART A TSAR 13.7 parts SR355 13.2 parts MicrodolTM 62.6 parts ThixinTM Paste 7.5 parts BaylithTM 3.0 parts
  • PART B LaropalTM A 81 44 parts EpodilTM L 53 parts TMG 3 parts Mechanical and Electrical Properties Tensile strength (N/mm 2 ) 5.4 Elongation at break (%) 0.7 Shore A hardness 62 Dielectric Strength (kV/mm) 22 Loss factor Room temperature 0.01 50°C 0.12 80°C 0.55 Permittivity Room temperature 4.2 50°C 6.6 80°C 10.2
  • the curable composition was also used to insulate an electrical splice in accordance with the procedure described in example 4. No formation of cracks was observed in the LWT test. Similar compositions with lower amounts of filler upto 20 parts by weight were also tested and did not show formations of cracks in the LWT test. It was further found that the insulation resistance (phase-to-phase and phase-to-water) obtained in the LWT test was more than 10000 Mega Ohms and comparable to commercial insulation resins.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Claims (15)

  1. Composition durcissable comprenant (i) un composé comportant au moins deux groupes α,β-insaturés et ayant un poids équivalent inférieur à 250 g/mol, (ii) un catalyseur capable d'amorcer une réaction de Michael et (iii) un donneur de Michael ayant un poids équivalent inférieur à 250 g/mol, et (iv) une charge en quantité comprise entre 10 et 65% en poids, ladite charge étant choisie dans le groupe constitué par le feldspath, la silice, les bulles de verre, le sable, le talc, l'hydroxyde d'aluminium, les poudres thermoplastiques, le kaolin, le dioxyde de silicium, les silicates d'aluminium, les silicates de magnésium, les charges polymères particulaires, les particules de céramique, le carbonate de magnésium et le carbonate de calcium.
  2. Composition durcissable selon la revendication 1 dans laquelle ledit donneur de Michael est un polyol acétoacétylé ayant un degré de conversion d'au moins 80% en moles, et lesdits groupes α,β-insaturés sont deux groupes carbonyle α,β-insaturés.
  3. Composition durcissable selon la revendication 2 dans laquelle ladite charge est présente en quantité d'au moins 50% en poids.
  4. Composition durcissable comprenant (i) un composé comportant au moins deux groupes α,β-insaturés et ayant un poids équivalent inférieur à 250 g/mol, (ii) un catalyseur capable d'amorcer une réaction de Michael et (iii) un donneur de Michael ayant un poids équivalent inférieur à 250 g/mol, et répondant à la formule III: W1-CH2-W2 w1 et W2 représentent chacun indépendamment des groupes attracteurs d'électrons.
  5. Composition durcissable selon la revendication 4 dans laquelle lesdits deux groupes α,β-insaturés sont deux groupes carbonyle α,β-insaturés et ledit donneur de Michael répond à la formule (IV) suivante: R-CO-CH2-CO-R1 dans laquelle R et R1 représentent chacun indépendamment des groupes aryloxy, alcoxy, alkyle ou aryle.
  6. Composition durcissable selon la revendication 5 dans laquelle lesdits deux groupes carbonyle α,β-insaturés sont des groupes acryliques ou méthacryliques, ou un mélange des deux.
  7. Polymère durci pouvant être obtenu par durcissement dune composition durcissable telle que définie dans la revendication 4.
  8. Paquet contenant les composants dune composition durcissable, ledit paquet comprenant deux compartiments, l'un desdits compartiments comprenant un donneur de Michael ayant un poids équivalent inférieur à 250 g/mol et un composé comportant au moins deux groupes α,β-insaturés et ayant un poids équivalent inférieur à 250 g/mol, et l'autre compartiment comprenant un catalyseur capable d'amorcer une réaction de Michael.
  9. Paquet selon la revendication 8 dans lequel au moins un desdits compartiments comprend en outre une charge organique ou minérale et/ou un épaississant.
  10. Paquet selon la revendication 9 dans lequel ledit épaississant est contenu dans ledit compartiment comprenant ledit catalyseur.
  11. Paquet selon la revendication 10 dans lequel ledit donneur de Michael répond à l'une des formules (I) à (III): (W1-CHR1-W2)x-P (W1-NH-W2)x-P W1-CH2-W2 W1-CH2-W2 formules dans lesquelles R1 représente un atome d'hydrogène, un groupe alkyle ou un groupe aryle;
    W1 et W2 représentent chacun indépendamment des groupes attracteurs d'électrons;
    P représente un résidu organique multivalent et x représente un nombre entier de 2 ou plus.
  12. Paquet selon la revendication 9 dans lequel ledit donneur de Michael est un polyol acétoacétylé ayant un degré de conversion d'au moins 80% en moles, ou un composé répondant à la formule (IV): R-CO-CH2-CO-R1 dans laquelle R et R1 représentent chacun indépendamment des groupes aryloxy, alcoxy, alkyle ou aryle.
  13. Procédé pour isoler des épissures électriques comprenant les étapes consistant à:
    a) se procurer un corps de moule contenant une épissure électrique;
    b) remplir ledit corps de moule avec une composition durcissable telle que définie dans l'une quelconque des revendications 1 à 6;
    c) laisser durcir ladite composition durcissable dans ledit corps de moule.
  14. Utilisation selon la revendication 13 dans laquelle ladite application électrique est une application électrique à tension faible ou moyenne.
  15. Utilisation selon la revendication 13 dans laquelle lesdits groupes α,β-insaturés sont des groupes carbonyle α,β-insaturés.
EP96944790A 1996-12-11 1996-12-11 Resine susceptible de durcir a temperature ambiante Expired - Lifetime EP0944664B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1996/019714 WO1998025989A1 (fr) 1996-12-11 1996-12-11 Resine susceptible de durcir a temperature ambiante

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EP0944664A1 EP0944664A1 (fr) 1999-09-29
EP0944664B1 true EP0944664B1 (fr) 2002-03-20

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DE60201877T2 (de) * 2001-12-21 2005-04-07 Dainippon Ink And Chemicals, Inc. Härtbare Harzzusammensetzungen und Verfahren zur Herstellung von Acrylatgruppen und substituierte Methacrylatgruppen enthaltende Oligomere
US8013068B2 (en) * 2003-01-02 2011-09-06 Rohm And Haas Company Michael addition compositions
WO2007064688A2 (fr) * 2005-11-30 2007-06-07 Ashland Licensing And Intellectual Property Llc Produits preimpregnes et surfaces solides traitees sur place preparees a partir de ceux-ci
DE102006055974A1 (de) * 2006-11-24 2008-05-29 Henkel Kgaa Reaktionsklebstoff
JP5518416B2 (ja) * 2009-10-01 2014-06-11 学校法人早稲田大学 ポリラジカル化合物の製造方法
CN105985724A (zh) 2011-10-07 2016-10-05 树脂核动力工业有限公司 可交联组合物
MY191989A (en) * 2012-03-09 2022-07-21 Polynt Composites Usa Inc Acetoacetyl thermosetting resin for zero voc gel coat
US9708444B2 (en) 2013-11-25 2017-07-18 Dow Global Technologies Llc Biodegradable aliphatic polyesters
PL3283587T3 (pl) 2015-04-17 2024-07-22 Allnex Netherlands B.V. Sieciowalne rma kompozycje i sieciowalne rma żywice do powłok łatwych do czyszczenia
AU2016247598B2 (en) 2015-04-17 2020-11-26 Allnex Netherlands B.V. Modified epoxy primer for improved adhesion of RMA crosslinkable coating compositions
EP3283583A1 (fr) 2015-04-17 2018-02-21 Allnex Netherlands B.V. Procédé de production d'une composition réticulable
EP3283556B1 (fr) 2015-04-17 2021-03-10 Allnex Netherlands B.V. Composition de revêtement de sol

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US4218515A (en) * 1979-05-14 1980-08-19 Heckles John S Acrylate-cyanoacetate-ureadiacetoacetamide-diacetoacetamide copolymers useful as protective surfaces
ZA852044B (en) * 1984-03-29 1985-11-27 Akzo Nv Liquid coating composition curable at ambient temperature
DE3572829D1 (en) * 1984-04-04 1989-10-12 Hoechst Ag Reaction product of olefinically unsaturated compounds with active hydrogen compounds, process for their preparation and 2-component coating systems based thereon
BR8606287A (pt) * 1985-12-19 1987-10-06 Cook Paint & Varnish Inc Processo para a preparacao de um polimero reticulado
JPH0491068A (ja) * 1990-08-06 1992-03-24 Nippon Kasei Chem Co Ltd ポリオール誘導体
US5459178A (en) * 1994-10-21 1995-10-17 Ashland Inc. Foundry mixes and their uses

Also Published As

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WO1998025989A1 (fr) 1998-06-18
JP2001505948A (ja) 2001-05-08
JP3804028B2 (ja) 2006-08-02
EP0944664A1 (fr) 1999-09-29
DE69620038D1 (de) 2002-04-25
DE69620038T2 (de) 2002-10-02

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